TW201703854A - Oxidation reactor, and method for producing oxides - Google Patents

Abstract

An oxidation reactor with which hydrocarbons can be oxidized efficiently in terms of both reaction efficiency and energy efficiency is provided. This oxidation reactor is equipped with: a liquid introduction channel through which a liquid containing a hydrocarbon as a reaction substrate is introduced; a gas introduction channel through which a gas comprising oxygen and ozone is introduced; a gas/liquid mixing part in which the liquid introduced through the liquid introduction channel is mixed with the gas introduced through the gas introduction channel; and a flow reactor, wherein the oxidation reactor is characterized in that either the inner wall of the flow reactor is a material containing iron, or the inside of the flow reactor is filled with a powder containing iron.

Description

Reactor for oxidation reaction, and method for producing oxide

The present invention relates to a reactor for an oxidation reaction and a method for producing an oxide using the reactor for the oxidation reaction. More specifically, it relates to a reactor for an oxidation reaction used for oxidizing a hydrocarbon in the presence of oxygen and ozone to obtain an oxide, and a method for producing an oxide using the reactor for the oxidation reaction. The present application claims the priority of Japanese Patent Application No. 2015-097581, filed on May 12, 2015 in Japan, the content of which is incorporated herein.

Oxidation is one of the most basic reactions in the organic chemical industry, and various oxidation methods have been developed. Patent Document 1 describes a method of oxidizing a radical-generating compound by molecular state oxygen or the like using a fat-soluble quinone imine compound as a catalyst. According to this method, a wide variety of substrates can be oxidized to obtain corresponding oxides. However, in this method, when a hydrocarbon such as a linear alkane is used as the reaction substrate, there is a problem that the yield is low.

On the other hand, the oxidation reaction of oxygen by a hydrocarbon is generally carried out by introducing a hydrocarbon of a raw material into a stirred tank type reactor and blowing oxygen or air into the reactor from the nozzle. However, in this method, heat transfer or gas-liquid mixing efficiency is low, and it may not be satisfactory in terms of reaction efficiency or energy efficiency.

Prior technical literature Patent literature

Patent Document 1 Japanese Patent Laid-Open Publication No. 2002-331242

Accordingly, it is an object of the present invention to provide a reactor for an oxidation reaction which can efficiently oxidize hydrocarbons. Still another object of the present invention is to provide a process for efficiently producing a corresponding oxide from a hydrocarbon.

As a result of intensive studies to solve the above problems, the inventors of the present invention have found that a reactor for an oxidation reaction can oxidize a hydrocarbon with high reaction efficiency, and the reactor for the oxidation reaction is provided with: a liquid introduction flow path of a hydrocarbon liquid of a reaction substrate; a gas introduction flow path for introducing oxygen and ozone; a gas-liquid mixing portion for mixing the liquid and the gas; and a specific flow reactor.

In the present invention, there is provided a reactor for an oxidation reaction comprising: a liquid introduction channel for introducing a liquid containing a hydrocarbon as a reaction substrate; and a gas for introducing oxygen and ozone; a gas introduction flow path; a gas-liquid mixing unit that mixes the liquid introduced from the liquid introduction channel and a gas introduced from the gas introduction channel; and a flow reactor, wherein the flow reactor has an inner wall A flow reactor of iron-containing material or a flow reactor filled with iron-containing powder inside.

In the reactor for oxidation reaction, it is preferred to provide a gas-liquid separator on the downstream side of the flow reactor.

In the reactor for oxidation reaction, it is preferable to provide a circulation flow path for recycling at least a part of the liquid separated by the gas-liquid separator to the gas-liquid mixing portion or the upstream portion thereof.

In the reactor for oxidation reaction, it is preferable to provide a circulation flow path for recycling at least a part of the gas separated by the gas-liquid separator to the gas-liquid mixing portion or the upstream portion thereof.

In the reactor for the oxidation reaction, it is preferred to provide a ruthenium compound introduction channel for introducing a quinone imine compound having a cyclic quinone imine skeleton on the upstream side of the flow reactor.

In the reactor for the oxidation reaction, it is preferred that the quinone imine compound having a cyclic quinone imine skeleton is a quinone imine compound represented by the following formula (I).

[wherein, n represents 0 or 1; X represents an oxygen atom or a -OR group (R represents a hydrogen atom or a protecting group of a hydroxyl group)].

Further, in the present invention, there is provided a method for producing an oxide, characterized in that a hydrocarbon is oxidized by coexistence of oxygen and ozone using the reactor for oxidation reaction to obtain a corresponding oxide.

That is, the present invention relates to the following.

[1] A reactor for an oxidation reaction, which is a reactor for an oxidation reaction comprising: a liquid for introducing a hydrocarbon containing a reaction substrate; a liquid introduction flow path; a gas introduction flow path for introducing a gas containing oxygen and ozone; a gas-liquid mixing portion for mixing the liquid introduced from the liquid introduction flow path and the gas introduced from the gas introduction flow path; and a flow reactor The flow reactor is characterized in that the inner wall is a flow reactor containing iron or a flow reactor filled with iron-containing powder.

[2] The reactor for oxidation reaction according to [1], wherein the iron-containing material on the inner wall of the flow reactor is a material containing a transition metal other than iron as a component other than iron.

[3] The reactor for oxidation reaction according to [1] or [2], wherein the iron-containing material of the inner wall of the flow reactor comprises a material selected from the group consisting of chromium, molybdenum, nickel, titanium, zirconium, vanadium, palladium, tungsten, At least one of the group of manganese and the group of manganese is a transition metal other than iron.

[4] The reactor for an oxidation reaction according to any one of [1] to [3] wherein the inner wall of the flow reactor is made of an alloy containing iron, and the alloy is chromium-iron alloy, nickel-iron alloy, or stainless steel. (SUS).

[5] The reactor for an oxidation reaction according to any one of [1] to [4] wherein in the flow reactor in which the iron-containing powder is filled, the iron-containing powder contains a transition other than iron. metal.

[6] The reactor for an oxidation reaction according to any one of [1] to [5] wherein, in the flow reactor in which the iron-containing powder is filled, the transition metal other than iron is selected from the group consisting of chromium, At least one of molybdenum, nickel, titanium, zirconium, vanadium, palladium, tungsten, and manganese.

[7] The reactor for an oxidation reaction according to any one of [1] to [6] wherein in the flow reactor in which the iron-containing powder is filled, iron-containing The powder is a powder in which an iron-containing alloy is pulverized, and the iron-containing alloy is a chromium-iron alloy, a nickel-iron alloy, or a stainless steel (SUS).

[8] The reactor for an oxidation reaction according to any one of [1] to [7] wherein the inner diameter of the flow reactor is preferably 3 mm or less (for example, 0.3 to 3 mm), more preferably 0.4 to 1.8 mm. Preferably, the flow rate is from 0.7 to 1.6 mm; the length of the flow reactor is preferably from 0.1 to 20 meters, more preferably from 0.3 to 10 meters.

[9] The reactor for an oxidation reaction according to any one of [1] to [8], wherein a gas-liquid separator is provided on a downstream side of the flow reactor.

[10] The reactor for oxidation reaction according to [9], comprising a circulation flow path for recycling at least a part of the liquid separated by the gas-liquid separator to the gas-liquid mixing portion or an upstream portion thereof.

[11] The reactor for an oxidation reaction according to [9] or [10], comprising a circulation flow path for recycling at least a part of the gas separated by the gas-liquid separator to the gas-liquid mixing portion or an upstream portion thereof .

[12] The reactor for an oxidation reaction according to any one of [1] to [11] wherein a sulfimine having a quinone imine compound having a cyclic quinone imine skeleton is provided on the upstream side of the flow reactor The compound is introduced into the flow path.

[13] The reactor for an oxidation reaction according to [12], wherein the quinone imine compound having a cyclic quinone imine skeleton is the quinone imine compound represented by the above formula (I).

[14] A method for producing an oxide, characterized in that the reactor for an oxidation reaction according to any one of [1] to [13] is used, and a hydrocarbon is oxidized in the presence of oxygen and ozone to obtain a corresponding oxide.

Since the reactor for oxidation reaction of the present invention has the above-described configuration, the hydrocarbon can be effectively oxidized, the catalyst cost can be eliminated, and the flow reactor due to the oxidation reaction is less deteriorated, so that it can be obtained with high productivity. Corresponding oxides.

1‧‧‧hydrocarbon supply flow path

2‧‧‧Oxygen introduction flow path

3‧‧‧Ozone generator

4‧‧‧ gas introduction flow path

5‧‧‧ gas-liquid mixing section (gas-liquid mixer)

6‧‧‧ gas-liquid mixture flow path

7‧‧‧Flow reactor

8‧‧‧Reaction mixture flow path

9‧‧‧ gas-liquid separator

10‧‧‧Liquid circulation flow path

11‧‧‧ gas circulation flow path

12‧‧‧Ozone Decomposer

13‧‧‧Exhaust line

14‧‧‧Imineimide compound introduction flow path

15‧‧‧Liquid introduction flow path

16‧‧‧Liquid recovery flow path

21‧‧‧ gas introduction pipeline (line A)

22‧‧‧Reaction liquid introduction pipeline (reaction liquid circulation pipeline; pipeline B)

23‧‧‧Flow reactor (line C)

24‧‧‧ gas-liquid mixing mixer

25‧‧‧ Receiver

50‧‧‧Microbubble generating device (microbubble generator)

51‧‧‧primary side (liquid introduction side)

52‧‧‧Air inlet (gas introduction side)

53‧‧‧Secondary side (gas-liquid mixture discharge side)

54‧‧‧Nozzles

55‧‧‧Diffuser

Fig. 1 is a schematic flow chart showing an example of a reactor for an oxidation reaction of the present invention.

Fig. 2 is a schematic view showing a reactor for an oxidation reaction in Example 1.

Fig. 3 is a schematic view showing an example of a microbubble generating device as a gas-liquid mixing portion.

[Formation of the Invention] [Reactor for oxidation reaction]

The reactor for an oxidation reaction according to the present invention includes a liquid introduction channel for introducing a liquid containing a hydrocarbon as a reaction substrate, a gas introduction channel for introducing a gas containing oxygen and ozone, and a liquid introduction channel introduced from the liquid introduction channel. a gas-liquid mixing unit in which a liquid is mixed with a gas introduced from the gas introduction passage; and a flow reactor characterized in that the flow reactor is a flow reactor whose inner wall is made of iron or is filled therein A flow reactor with iron-containing powder.

Fig. 1 is a schematic flow chart showing an example of a reactor for an oxidation reaction of the present invention. However, the present invention is not limited to the reactor for oxidation reaction described in Fig. 1 . The following is a description of Fig. 1.

In the first drawing, the hydrocarbon as the reaction substrate is supplied to the gas-liquid mixing unit (gas-liquid mixer) 5 through the hydrocarbon supply channel 1. The above hydrocarbons may also be supplied in the form of a solution dissolved in a solvent, as needed. On the other hand, oxygen or an oxygen-containing gas (for example, air or the like) is supplied to the ozone generator 3 through the oxygen introduction channel 2, and a part of the oxygen is converted into ozone, and a mixed gas system including oxygen and ozone is introduced into the flow path through the gas. 4 is supplied to the gas-liquid mixing section 5. An inert gas such as nitrogen may be mixed into a mixed gas containing oxygen and ozone, and then supplied to the gas-liquid mixing unit 5.

The gas-liquid mixing unit (gas-liquid mixer) 5 is not particularly limited as long as it has a structure in which the gas and the liquid are mixed to form a gas-liquid mixture, and the mixing efficiency of the gas and the liquid and the dispersibility of the bubbles in the liquid are not particularly limited. The viewpoint of the like is preferably a microbubble generating device (microbubble generator). The microbubble refers to a bubble having a bubble diameter of 50 μm or less (generally 10 to 40 μm) at the time of production. The microbubbles containing oxygen and ozone become soluble in the liquid, so that the oxidation reaction can be efficiently performed.

The microbubble generating device can be roughly classified into two types of a pressurized dissolution mode and a two-phase flow swirling mode, and in the present invention, any of the microbubble generating devices can be used. Further, a commercially available microbubble generating device can be used. A schematic view showing an example of the microbubble generating device (a view from the side) is shown in Fig. 3, but the present invention is not limited thereto. In Fig. 3, 50 is a microbubble generating device (microbubble generator), 51 is a primary side (liquid introduction side), 52 is an intake port (gas introduction side), and 53 is a secondary side (gas-liquid mixture discharge side) ), 54 is the nozzle and 55 is the diffuser. The arrows in the figure indicate the direction in which liquids and gases are introduced. A cylindrical flow path is provided from the primary side 51 to the secondary side 53 with the inner diameter of the passage being tapered, from the intake port 52 The flow path of the gas is connected to the tapered portion (the front end portion of the nozzle 54) in the vertical direction. The liquid introduced from the primary side 51 is violently ejected from the nozzle 54 through the narrowest portion to the diffuser 55 along with the gas introduced from the intake port 52 (including a mixed gas of oxygen and ozone), thereby generating a liquid containing microbubbles. The resulting microbubble containing liquid system is discharged from the secondary side 53. The discharge front end of the secondary side 53 may also be provided with a tank in which static water is stored. The liquid introduction channel of the primary side 51 and the inner diameter of the gas-liquid mixture flow path of the secondary side 53 in the microbubble generating device can be appropriately set in consideration of the production efficiency of the microbubbles, for example, 10 to 1000 mm, preferably. It is 15~350 mm. Further, the inner diameter of the gas introduction passage of the intake port 52 can be appropriately set in consideration of the production efficiency of the microbubbles, and the like, and is, for example, 2 to 300 mm, preferably 4 to 150 mm.

The gas-liquid mixture portion 5 (for example, the gas-liquid mixture flow path of the secondary side 53 of the microbubble generating device 50) is connected to the gas-liquid mixture flow path 6 which is connected to the flow reactor 7. The gas-liquid mixing section 5 can also be directly connected to the flow reactor 7.

The material of the gas-liquid mixture (gas-liquid mixing unit 5) is not particularly limited as long as it is inert to the gas or liquid used for the reaction, and may be, for example, a resin [Teflon (registered trademark), Diflon, a fluorine-based resin such as polyvinylidene fluoride, a polyester resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin, a polyamide resin, a polyimide resin, etc., glass, Metal (titanium, alloys such as stainless steel, etc.), etc. When the material of the gas-liquid mixer is made of metal or the like, resin coating or glass lining may be applied to the portion in contact with the gas-liquid mixture.

The mixed gas containing oxygen and ozone supplied to the gas-liquid mixing unit 5 and the liquid containing the hydrocarbon as the reaction substrate are discharged into the gas-liquid mixture in the gas-liquid mixer, and are discharged through the gas-liquid mixture flow path 6 to flow reaction. Inside the device 7. In the flow reactor 7, the hydrocarbon as a reaction substrate is oxidized to form a corresponding oxide.

The reaction mixture discharged from the flow reactor 7 is introduced into the gas-liquid separator 9 through the reaction mixture flow path 8, and is separated into a gas and a liquid. The flow reactor 7 can also be directly connected to the gas-liquid separator 9. The separated gas is introduced into the ozone decomposer 12, and is discharged to the outside through the exhaust gas line 13. At least a portion of the separated gas is returned to the upstream portion of, for example, the ozone generator 3 through the gas circulation flow path 11 as needed, thereby being recycled in the reaction system. On the other hand, at least a part of the liquid separated by the gas-liquid separator 9 can be recirculated to the gas-liquid mixing portion 5 by the liquid introduction flow path 15 through the liquid circulation flow path 10 using, for example, a pump. Further, the liquid separated by the gas-liquid separator 9 can be recovered by the liquid recovery flow path 16. Further, depending on the demand, on the upstream side of the flow reactor 7, preferably the gas-liquid mixing portion 5 or a portion thereof further upstream, a crucible for introducing a quinone imine compound having a cyclic quinone imine skeleton to be described later is provided. The imine compound is introduced into the flow path 14.

[Flow reactor]

The reactor for oxidation reaction of the present invention is characterized in that the flow reactor is a flow reactor in which the inner wall is made of iron or a flow reactor in which iron-containing powder is filled.

The inner wall of the flow reactor is in the case of a material containing iron, at least a part of which needs to be in contact with the gas-liquid mixture. That is, a part of the inner wall of the flow reactor may be subjected to resin coating, glass lining or the like, but it is preferably not implemented based on the viewpoint of oxidation reaction efficiency. An example of the case where the inner wall of the flow reactor is a material containing iron is a case where the material of the entire flow reactor (the material of the flow reactor itself) is a material containing iron.

When the inner wall of the flow reactor is made of a material containing iron, the material containing iron may be a material containing a transition metal other than iron as a component other than iron. That is, the flow reactor may also be a material containing a transition metal other than iron and iron. The transition metal other than iron is not particularly limited, and examples thereof include chromium, molybdenum, nickel, titanium, zirconium, vanadium, palladium, tungsten, manganese, and the like. Further, one of the transition metals other than the iron may be contained, or two or more types may be contained in the flow reactor.

Specific examples of the case where the inner wall of the flow reactor is a material containing iron, for example, the iron-containing material described above is an alloy containing iron or a resin containing iron (for example, Teflon (registered trademark), A fluorine resin such as Diflon, a polyester resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin, a polyamide resin, a polyimide resin, or the like. At this time, the material of the outer wall (portion other than the inner wall) of the flow reactor is not particularly limited.

Examples of the iron-containing alloy include an alloy containing a transition metal (for example, chromium) other than iron and the like such as a chromium-iron alloy, a nickel-iron alloy, or a stainless steel (SUS). In addition, stainless steel (SUS) means iron or chromium as a main component, and may further contain nickel or carbon as another metal. Divided alloy steel. For example, SUS301, SUS302, SUS303, SUS304, SUS305, SUS316, SUS317, SUS329J1, SUS403, SUS405, SUS420, SUS430, SUS430LX, SUS630, etc. are known.

The flow reactor is in the case of a flow reactor in which the iron-containing powder is filled, and the material of the flow reactor is not particularly limited as long as it is inert to the gas or liquid used for the reaction and does not dissolve. For example, a fluorine resin such as a resin [Teflon (registered trademark) or Diflon, a polyester resin, a polyolefin resin, a polycarbonate resin, a polystyrene resin, a polyamide resin, or a polyruthenium can be used. An amine resin or the like], an inorganic oxide (such as cerium oxide), glass, a metal (such as an alloy such as titanium or stainless steel). Among them, Teflon (registered trademark) is preferred in that the deterioration due to the oxidation reaction is small. When the flow reactor is made of metal or the like, a resin coating or a glass liner may be applied to a portion in contact with the gas-liquid mixture.

Further, the flow reactor is a flow reactor in which the inner wall is made of iron and does not contain iron-containing powder or oxidation catalyst on the inner side thereof, and the flow reactor is not clogged by particles or the like, and can be High manufacturing efficiency oxidizes hydrocarbons.

As the iron-containing powder filled in the flow reactor, a transition metal other than iron may also be contained. The transition metal other than iron is not particularly limited, and examples thereof include chromium, molybdenum, nickel, titanium, zirconium, vanadium, palladium, tungsten, manganese, and the like. In addition, one type of transition metals other than such iron may be contained, and two or more types may be contained.

Specific examples of the iron-containing powder include those obtained by grinding an iron-containing alloy into a powder. Examples of the iron-containing alloy include an alloy containing a transition metal (for example, chromium) other than iron and the like such as a chromium-iron alloy, a nickel-iron alloy, or a stainless steel (SUS). Further, in terms of stainless steel (SUS), it is as described above.

The particle diameter of the iron-containing powder is not particularly limited, but is preferably 0.1 μm to 500 μm, more preferably 1 μm to 100 μm, still more preferably about 5 μm to 50 μm. Furthermore, the filling of the interior of the flow reactor with the iron-containing powder can be carried out by methods well known or known in the art.

In the present invention, it can be inferred that the iron-containing material on the inner wall of the flow reactor or the iron-containing powder in the flow reactor functions as a catalyst when the hydrocarbon is oxidized. Among the iron-containing materials or iron-containing powders, stainless steel (SUS) has high resistance to hydrocarbons, reaction solvents, oxidation catalysts, ozone, etc. used as a reaction substrate for oxidation reaction, and less deterioration due to oxidation reaction. . Therefore, the productivity of the oxide can be improved.

The temperature control of the flow reactor may be, for example, a method in which the flow reactor is configured as a multi-tube structure to circulate a heat medium or a refrigerant to the inner tube or the outer tube, or a method of immersing the flow reactor in a heat medium bath or a refrigerant bath. Waiting for it. Further, the temperature of the flow reactor is preferably set to be the same as the reaction temperature of the oxidation reaction item described later.

The inner diameter of the flow reactor is not particularly limited, but is preferably 3 mm or less (for example, 0.3 to 3 mm), more preferably 0.4 to 1.8 mm, and still more preferably 0.7 to 1.6 mm. The length of the flow reactor can be appropriately selected depending on the reaction rate and the like, and is preferably from 0.1 to 20 meters, more preferably from about 0.3 to 10 meters.

[oxygen and ozone]

In the present invention, oxygen as an oxidizing agent is used in an oxidation reaction in the presence of ozone. That is, a mixed gas containing oxygen and ozone gas is used for the oxidation reaction. By using oxygen as an oxidizing agent together with ozone, hydrogen abstraction from a hydrocarbon as a reaction substrate can be promoted, and a radical reaction can be activated. Therefore, under mild conditions, the oxidation reaction can also be promoted. The amount of the ozone gas in the mixed gas of oxygen and ozone gas is, for example, about 0.1 to 10% by volume based on the viewpoint of reactivity and economy. Oxygen and ozone can also be used by diluting to an appropriate concentration by an inert gas such as nitrogen. The concentration of oxygen in the mixed gas containing oxygen and ozone gas is, for example, 5% by volume or more, preferably 10% by volume or more, more preferably 15% by volume or more, and the upper limit thereof is, for example, 99.9% by volume, preferably 80% by volume. More preferably, it is 50% by volume, and particularly preferably 25% by volume.

[hydrocarbon (reaction substrate)]

In the method for producing an oxide in the present invention, a hydrocarbon can be used as a reaction substrate. Examples of the hydrocarbon include an aliphatic hydrocarbon, an alicyclic hydrocarbon, and an aromatic hydrocarbon.

Examples of the aliphatic hydrocarbons include ethane, propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane, dodecane, tridecane, and tetradecene. Linear, alkane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane, eicosane, eicosane, docosane, heptacosane, tetracosane, etc. An alkane (for example, a linear alkane having a carbon number of 3 to 30, preferably 4 to 20, etc.); 2-methylpropane, 2-methylbutane, 2,2-di Methylpropane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, 2-methylhexane, 3-methylhexane, 3,4-dimethyl a branched alkane such as an alkane or a 3-methyloctane (for example, a branched chain alkane having a carbon number of 3 to 30, preferably 4 to 20); propylene, isobutylene, 1-pentene, 1-hexene, Linear or branched alkene of 2-hexene, 1-heptene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1,4-hexadiene Or an alkadiene (for example, a linear or branched alkene or an alkadiene having a carbon number of 3 to 30, preferably 4 to 20).

Examples of the alicyclic hydrocarbons include cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, cyclodecane, cyclodecane, cyclododecane, and ring fourteen. a naphthenic such as an alkane, a cyclohexadecane or a cyclotriaconane [a cycloalkane of 3 to 30 members (preferably 5 to 30 members, particularly preferably 5 to 20 members)]; cyclopropene, cyclobutene, a cycloolefin such as cyclopentene, cyclooctene, cyclohexene, cycloheptene or cyclododecene [3 to 30 members (preferably 3 to 20 members, particularly preferably 3 to 12 members)) a cycloalkanadiene such as cyclopentadiene, 1,3-cyclohexadiene or 1,5-cyclooctadiene; a cycloalkanetriene such as cyclooctanetriene; decahydronaphthalene or bicyclo [2.2. 0] hexane, bicyclo [2.2.2] octane, bicyclo [3.2.1] octane, bicyclo [4.3.2] undecane, bicyclo [3.3.3] undecane, norbornane, norbornene , tricyclo[5.2.1.0 ^2,6 ]decane, tricyclo[6.2.1.0 ^2,7 ]undecane, adamantane, perhydroanthracene, perhydroquinonenaphthalene, perhydrophenanthrene, perhydroanthracene, perhydrogen 2 to 4 ring bridged cyclic hydrocarbons such as hydrazine.

Examples of the aromatic hydrocarbons include aromatic hydrocarbons having 6 to 20 carbon atoms such as benzene, naphthalene, and anthracene.

In addition, the hydrocarbon may have one or two or more groups selected from the group consisting of an aliphatic hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group as a substituent.

The aliphatic hydrocarbon group is a group (monovalent or divalent or higher aliphatic hydrocarbon group) in which one or two or more hydrogen atoms are removed from the structural formula of the aliphatic hydrocarbon. The monovalent aliphatic hydrocarbon group may, for example, be a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a secondary butyl group, a tertiary butyl group, a pentyl group, a hexyl group or an octyl group. a linear or branched alkyl group having 1 to 10 carbon atoms such as a mercapto group; an alkenyl group having 2 to 10 carbon atoms such as a vinyl group, an isopropenyl group or a 1-butenyl group; an ethynyl group and a propynyl group; Such as a carbon number of 2 to 10 propynyl groups. Examples of the divalent aliphatic hydrocarbon group include a linear or branched carbon number of 1 to 10 such as a methylene group, an exoethyl group, a propylidene group, a trimethylene group, an isopropylidene group, and a butylene group. The alkyl group and the like. The trivalent aliphatic hydrocarbon group may, for example, be an alkylene group having 1 to 10 carbon atoms such as a 1,2,3-propane triyl group.

Examples of the alicyclic hydrocarbon group include a group (monovalent or divalent or higher alicyclic hydrocarbon group) in which one or two or more hydrogen atoms are removed from the structural formula of the alicyclic hydrocarbon. Examples of the alicyclic hydrocarbon group include a cycloalkyl group such as a cyclopentyl group and a cyclohexyl group; a cycloalkenyl group such as a cyclopentenyl group or a cyclohexenyl group; an adamantyl-1-yl group and a norbornane-2; a bridged cyclic hydrocarbon group such as a group or a norbornane-7,7-diyl group or the like.

The aromatic hydrocarbon group is a group (monovalent or divalent or higher aromatic hydrocarbon group) in which one or two or more hydrogen atoms are removed from the structural formula of the aromatic hydrocarbon. Examples of the aromatic hydrocarbon group include a phenyl group, a 1-naphthyl group, a 1,2-phenylene group, a 1,3-phenylene group, and a 1,4-phenylene group.

Further, the hydrocarbon also includes a compound in which an alicyclic hydrocarbon and an aromatic hydrocarbon are condensed in the form of two carbon atoms in total. Examples of such a compound include decane, tetrahydronaphthalene, anthracene, anthraquinone, and the like.

The hydrocarbon may have one or two or more substituents other than the hydrocarbon group in the range which does not impair the reaction, and may or may not be contained.

In the present invention, the carbon number of the hydrocarbon as the reaction substrate is not particularly limited, but is preferably about 2 to 30, more preferably 3 to 25, still more preferably 4 to 20.

In the present invention, preferred hydrocarbons include propane, butane, pentane, hexane, heptane, octane, decane, decane, undecane, dodecane, tridecane, and ten. a linear alkane such as tetradecane, pentadecane, hexadecane, heptadecane, octadecane, nonadecane or eicosane (for example, a linear chain having a carbon number of 3 to 30, preferably 4 to 20) Alkane, etc.; 2-methylpropane, 2-methylbutane, 2,2-dimethylpropane, 2-methylpentane, 3-methylpentane, 2,3-dimethylbutane, a branched alkane such as 2-methylhexane, 3-methylhexane, 3,4-dimethylhexane or 3-methyloctane (for example, a carbon number of 3 to 30, preferably 4 to 20) a branched alkane or the like; a cycloalkane such as cyclopentane or cyclohexane; a cycloalkane of 3 to 30 members (preferably 5 to 30 members, particularly preferably 5 to 20 members); toluene, o. Xylene, m-xylene, p-xylene, o-tertiary butyl toluene, m-terphenyl butyl toluene, p-tert-butyltoluene, 1-ethyl-4-methylbenzene, 1-ethyl-3- Methylbenzene, 1-isopropyl-4-methylbenzene, 1-tributyl-4-methylbenzene, mesitylene, meta-trimethylbenzene, tetramethylbenzene, methylnaphthalene, dimethylnaphthalene, Methyl hydrazine, 4,4'-dimethylbiphenyl, B An aromatic group having one or two or more alkyl groups (for example, an alkyl group having 1 to 6 carbon atoms) bonded to an aromatic ring such as benzene, propylbenzene, butylbenzene or 1,4-diethylbenzene A compound obtained by condensing an alicyclic hydrocarbon such as tetrahydronaphthalene or an anthracene with an aromatic hydrocarbon in the form of a total of two carbon atoms.

The hydrocarbon which is the reaction substrate can be used by diluting it to a suitable concentration by a solvent inert to the oxidation reaction. However, due to oxidation Since the oxygen of the agent is used in the presence of ozone, the oxidation reaction can be carried out even if the solvent is not substantially used. In the case where the solvent is not substantially used, it is not necessary to separate the oxide which is the reaction product from the solvent, and the complexity of the manufacturing process can be overcome.

Examples of the solvent include organic acids such as acetic acid and propionic acid; nitriles such as acetonitrile, propionitrile and benzonitrile; formamide, acetamide, dimethylformamide, and dimethylamine. Amidoxime such as guanamine; halogenated hydrocarbon such as chloroform, dichloromethane, dichloroethane, carbon tetrachloride, chlorobenzene or trifluoromethylbenzene; nitrobenzene, nitromethane, nitroethane, etc. a nitro compound; an ester of ethyl acetate or butyl acetate; and a mixed solvent thereof.

From the viewpoint of the reaction efficiency, the concentration of the hydrocarbon as the reaction substrate in the liquid supplied to the gas-liquid mixing portion 5 (or the flow reactor 7) is preferably 30% by weight or more, more preferably 50% by weight or more, and still more preferably 85%. More preferably, the weight is at least 95% by weight.

[Indoleimine compound having a cyclic quinone imine skeleton]

In the present invention, in order to further promote the oxidation reaction, a quinone imine compound having a cyclic quinone imine skeleton may be used as a promoter. In other words, a ruthenium compound introduction channel for introducing a quinone imine compound having a cyclic quinone imine skeleton may be provided on the upstream side of the flow reactor of the oxidation reaction reactor.

As the quinone imine compound having a cyclic quinone imine skeleton, various known quinone imine compounds having a cyclic quinone imine skeleton can be used. The quinone imine compound having a cyclic quinone imine skeleton may, for example, be a cyclic quinone imine skeleton represented by the above formula (I).

In the formula (I), the bond of the nitrogen atom to X is a single bond or a double bond. The above quinone imine compound may have a plurality of cyclic quinone imine skeletons represented by the formula (I) in the molecule. Further, in the case where X is a -OR group and R is a protective group of a hydroxyl group, the above-described quinone imine compound may also have a moiety other than R in a plurality of cyclic quinone imine skeletons via R (N-oxy cyclic oxime) Imine skeleton) bonding.

Examples of the protective group of the hydroxyl group represented by R include an alkyl group (e.g., a C _1-4 alkyl group such as a methyl group or a tertiary butyl group), an alkenyl group (e.g., an allyl group), and a cycloalkane. a group (e.g., cyclohexyl, etc.), an aryl group (e.g., 2,4-dinitrophenyl, etc.), an aralkyl group (e.g., benzyl, 2,6-dichlorobenzyl, 3-bromobenzyl, 2-nitrobenzyl, triphenylmethyl, etc.; substituted methyl group (eg methoxymethyl, methylthiomethyl, benzyloxymethyl, tert-butoxymethyl) , 2-methoxyethoxymethyl, 2,2,2-trichloroethoxymethyl, bis(2-chloroethoxy)methyl, 2-(trimethyldecyl)ethoxy Methyl, etc., substituted ethyl (eg 1-ethoxyethyl, 1-methyl-1-methoxyethyl, 1-isopropoxyethyl, 2,2,2-trichloro) Ethyl, 2-methoxyethyl, etc.), tetrahydropyranyl, tetrahydrofuranyl, and 1-hydroxyalkyl, etc. (eg 1-hydroxyethyl, 1-hydroxyhexyl, 1-hydroxyindenyl, 1 a hydroxyl group of a -hydroxyhexadecyl group, a 1-hydroxy-1-phenylmethyl group, or the like, forming a group of an acetal or a hemiacetal group; an anthracenyl group (for example, a fluorenyl group, an ethyl fluorenyl group, a propyl fluorenyl group, a butyl fluorenyl group, an isobutyl fluorenyl group) Wuxu , Trimethyl acetyl group, hexyl acyl, acyl heptyl, octyl acyl, acyl nonyl, decyl acyl, acyl lauryl, myristyl acyl, acyl palmitate, stearyl acyl such as C _1-20 fatty An aliphatic or unsaturated fluorenyl group such as an aliphatic or unsaturated fluorenyl group; an alicyclic fluorenyl group such as a cyclopentanecarbonyl group such as a cyclopentanecarbonyl group or a cyclohexanecarbonyl group; a benzamidine group or a naphthoquinone group; An aromatic sulfhydryl group or the like); a sulfonyl group (methanesulfonyl group, an ethylsulfonyl group, a trifluoromethanesulfonyl group, a benzenesulfonyl group, a p-toluenesulfonyl group, a naphthalenesulfonyl group, etc.), an alkane An oxycarbonyl group (for example, a C _1-4 alkoxy-carbonyl group such as a methoxycarbonyl group, an ethoxycarbonyl group or a tertiary oxycarbonyl group) or an aralkyloxycarbonyl group (for example, a benzyloxycarbonyl group, P-methoxybenzyloxycarbonyl, etc., substituted or unsubstituted amine carbenyl (eg, amine carbaryl, methylamine, phenylamine, phenylaminomethyl, etc.), from inorganic acids (such as sulfuric acid, nitric acid, phosphoric acid, boric acid, etc.) to remove the OH group, dialkylthiophosphino (such as dimethylphosphinyl), diarylthiophosphino (such as diphenylphosphine) Base, etc., substituted decyl group (eg Trimethyldecyl, tertiary butyl dimethyl decyl, trityl decyl, triphenyl decyl, etc.).

In the case where X is a -OR group, R which is bonded to a portion other than R (N-oxy cyclic quinone imine skeleton) of a plurality of cyclic quinone imine skeletons via R may be mentioned. For example, ethanediyl, propylenediyl, butyl fluorenyl, pentane fluorenyl, hexamethylene fluorenyl, phthalic acid, m-xylylene, p-xylylene a polyvalent hydrocarbon group of a polycarboxylic acid fluorenyl group; a carbonyl group; a methylene group, an ethylene group, an isopropylidene group, a cyclopentylene group, a cyclohexylene group, a benzylidene group or the like (especially an acetal group capable of forming an acetal with two meridians) Base) and so on.

Preferably, R comprises, for example, a hydrogen atom; a group which can form an acetal or a hemiacetal with a hydroxyl group; and can remove OH from an acid such as a carboxylic acid, a sulfonic acid, a carbonic acid, an aminocarboxylic acid, a sulfuric acid, a phosphoric acid, or a boric acid by hydrolysis. A hydrolyzable protecting group which is derivatized by a group such as a thiol group, a sulfhydryl group, an alkoxycarbonyl group or an amine formazan group.

In the formula (I), n represents 0 or 1. That is, in the formula (I), when n is 0, it represents a cyclic quinone imine skeleton of 5 members, and when n is 1, it represents a cyclic quinone imine skeleton of 6 members.

A representative example of the above quinone imine compound is a quinone imine compound represented by the following formula (1). In the formula (1), n represents 0 or 1. X represents an oxygen atom or an -OR group (R represents a hydrogen atom or a protecting group of a hydroxyl group). R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, and a Substituted oxycarbonyl, decyl or decyloxy. At least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a double bond or form a ring together with a carbon atom constituting the cyclic quinone imine skeleton. a double formed by bonding at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ or R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ The ring or the ring formed by the carbon atom constituting the cyclic quinone imine skeleton may be bonded to one or two or more cyclic quinone imine groups represented by the following formula (1).

The halogen atoms in the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ of the quinone imine compound represented by the formula (1) include iodine, bromine, chlorine, and a fluorine atom. The alkyl group contains, for example, methyl, ethyl, propyl, isopropyl, butyl, isobutyl, secondary butyl, tert-butyl, hexyl, decyl, dodecyl, tetradecyl, hexadecan. A linear or branched alkyl group having a carbon number of from 1 to 30 (particularly from 1 to 20 carbon atoms).

The aryl group includes, for example, a phenyl group, a naphthyl group or the like; and the cycloalkyl group contains, for example, a cyclopentyl group, a cyclohexyl group or the like. The alkoxy group includes, for example, a methoxy group, an ethoxy group, an isopropoxy group, a butoxy group, a tertiary butoxy group, a hexyloxy group, an octyloxy group, a decyloxy group, a dodecyloxy group, a tetradecyloxy group. An alkoxy group having a carbon number of from 1 to 30 (especially 1 to 20 carbon atoms) such as octadecyloxy.

The substituted oxycarbonyl group may, for example, be a methoxycarbonyl group, an ethoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, a tertiary butoxycarbonyl group, a hexyloxycarbonyl group or a decyloxycarbonyl group. a C _1-30 alkoxycarbonyl group such as a hexadecyloxycarbonyl group (especially a C _1-20 alkoxy-carbonyl group); a cycloalkyloxycarbonyl group such as a cyclopentyloxycarbonyl group or a cyclohexyloxycarbonyl group (especially 3 to 20 membered cycloalkyloxycarbonyl); aryloxycarbonyl group such as phenyloxycarbonyl, naphthyloxycarbonyl or the like (especially C _6-20 aryloxy-carbonyl); benzyloxycarbonyl group An aralkyloxycarbonyl group (especially a C _7-21 aralkyloxy-carbonyl group) or the like.

The fluorenyl group includes, for example, a methyl group, an ethyl group, a propyl group, a butyl group, a butyl group, an isobutyl group, a pentyl group, a trimethylethyl group, a hexyl group, a decyl group, a fluorenyl group, a lauryl group, a nutmeg. An aliphatic saturated or unsaturated fluorenyl group such as a C _1-30 aliphatic fluorenyl group (especially a C _1-20 aliphatic fluorenyl group) such as a mercapto group, a palmitoyl group or a stearyl group; An alicyclic fluorenyl group such as a cycloalkylcarbonyl group such as a pentanecarbonyl group or a cyclohexanecarbonyl group; an aromatic fluorenyl group such as a benzamidine group or a naphthylmethyl group;

The oxime group includes, for example, a methyl methoxy group, an ethoxy group, a propyl methoxy group, a butoxy group, an isobutyl oxy group, a pentyloxy group, a trimethyl ethoxy group, a hexanyloxy group. C _1-30 aliphatic decyloxy group (especially C _1-20 fat) such as octyloxy, decyloxy, lauryloxy, myristyloxy, palmitoyloxy, stearyloxy An aliphatic or saturated methoxy group such as an aliphatic or unsaturated methoxy group; an alicyclic oxime such as a cyclopentanylcarbonyloxy group or a cycloalkylcarbonyloxy group such as a cyclopentanylcarbonyloxy group; An oxy group; an aromatic decyloxy group such as a benzyl methoxy group or a naphthyl methoxy group.

a ring in which at least two of the substituents R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other and to a carbon atom constituting the cyclic quinone imine skeleton, for example, 5~12 member ring (extra good for 6~10 member ring). The aforementioned ring system includes a hydrocarbon ring, a hetero ring, and a condensed hetero ring. Specific examples of such a ring include a non-aromatic alicyclic ring (a cycloalkenyl ring such as a cyclohexane ring or a cyclohexene ring which may have a substituent such as a cyclohexane ring). A non-aromatic bridging ring (such as a bridged hydrocarbon ring which may have a substituent such as a 5-northene ring) or an aromatic ring (containing a condensed ring) (a benzene ring or a naphthalene ring) which may have a substituent. Examples of the substituent which the ring may have include an alkyl group, a halogen alkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, a decyl group, a decyloxy group, a nitro group, a cyano group, and an amine group. , halogen atoms, etc.

a double formed by bonding at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ or R ⁶ or R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ The ring or the ring formed by the carbon atom constituting the cyclic quinone imine skeleton may be bonded to one or more cyclic quinone imine groups represented by the above formula (1), for example, R. ^When R ² , R ³ , R ⁴ , R ⁵ or R ⁶ is an alkyl group having 2 or more carbon atoms, the cyclic quinone imine may be formed by including two adjacent carbon atoms constituting the alkyl group. base. Further, when at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ are bonded to each other to form a double bond, the cyclic quinone imine group may be formed by including the double bond. Further, at least two of R ¹ , R ² , R ³ , R ⁴ , R ⁵ and R ⁶ may be bonded to each other to form a cyclic quinone imine together with a carbon atom constituting the cyclic quinone imine skeleton. base.

A preferred quinone imine compound comprises a compound represented by the following formula. Wherein R ¹¹ to R ¹⁶ are the same or different and each represents a hydrogen atom, a halogen atom, an alkyl group, an aryl group, a cycloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a substituted oxycarbonyl group, a fluorenyl group, or Alkoxy. R ¹⁷ to R ²⁶ are the same or different and each represents a hydrogen atom, an alkyl group, a haloalkyl group, a hydroxyl group, an alkoxy group, a carboxyl group, a hydroxy-substituted oxycarbonyl group, a decyl group, a decyloxy group, a nitro group, a cyano group, Amine group, or a halogen atom. In the case of R ¹⁷ to R ²⁶ , adjacent groups may be bonded to each other to form 5 as shown in the formula (1c), (1d), (1e), (1f), (1h), or (1i) Cyclic quinone imine skeleton of 6 members or 6 members. A represents a methylene group or an oxygen atom. The X system is the same as described above.

As the halogen atom, alkyl group, aryl group, cycloalkyl group, hydroxyl group, alkoxy group, carboxyl group, substituted oxycarbonyl group, fluorenyl group, and decyloxy group of the substituents R ¹¹ to R ¹⁶ , R ¹ described above can be exemplified. The corresponding bases in ~R ⁶ are the same.

The alkyl group of the substituent R ¹⁷ to R ²⁶ may, for example, be the same alkyl group as the above-exemplified alkyl group (preferably an alkyl group having about 1 to 6 carbon atoms, particularly preferably a lower alkyl group having 1 to 4 carbon atoms). The halogenated alkyl group may, for example, be a halogenated alkyl group having a carbon number of from 1 to 4 such as a trifluoromethyl group; and the alkoxy group may be the same alkoxy group as described above (especially a low carbon number of about 1 to 4). Alkoxy); as the substituted oxycarbonyl group, the same substituted oxycarbonyl group as described above (alkoxycarbonyl group, cycloalkyloxycarbonyl group, aryloxycarbonyl group, aralkyloxycarbonyl group) can be exemplified. Wait). Further, examples of the fluorenyl group include the same fluorenyl group (aliphatic saturated or unsaturated fluorenyl group, acetamidine group, alicyclic fluorenyl group, aromatic fluorenyl group, and the like) as described above; The same oxime oxygen group as the above (aliphatic saturated or unsaturated decyloxy group, acetamethylene oxy group, alicyclic decyloxy group, aromatic decyloxy group, etc.). Examples of the halogen atom include fluorine, chlorine, and bromine atoms. The substituent R ¹⁷ to R ^{26 is} particularly preferably a hydrogen atom, a lower alkyl group having a carbon number of from 1 to 4, a carboxyl group, a substituted oxycarbonyl group, a nitro group or a halogen atom.

Further, in the present invention, since oxygen as an oxidizing agent is used in the presence of ozone, the hydrocarbon as a reaction substrate can be oxidized with an extremely excellent oxidizing power. Therefore, even in the solubility parameter of the bismuth imide compound according to the method of Fedors [SP value; the evaporation energy of the oxygen atom (-O-) constituting the ester bond is 3350 J/mol, and the molar volume is 3.8 cm ³ /mol. The value at the temperature (25 ° C)] is, for example, more than 26 [(MPa) ^1/2 ] (preferably more than 26 [(MPa) ^1/2 ] and 40 [(MPa) ^1/2 ] or less) The reaction can be carried out rapidly without a solvent, and an oxide can be obtained efficiently. In addition, the SP value can be based on the method described in the literature [Ref. RFFedors, Polym. Eng. Sci., 14(2), 147 (1974); EAGrulke, Polymer Handbook, VII/675; Harahara Yuki, Coating Technology, 3, 129 (1987)] Seek.

Among the preferred quinone imine compounds, a representative example of a compound having a cyclic quinone imine skeleton of 5 members includes quinone imine N-hydroxysuccinate and hydrazine N-hydroxy-α-methyl succinate. Imine, N-hydroxy-α, α-dimethylsuccinimide, N-hydroxy-α, β-dimethylsuccinimide, N-hydroxy-α, α, β, β-four Succinimide methyl succinate, succinimide N-hydroxymaleate, N-hydroxyhexahydrophthalimide, N,N'-dihydroxycyclohexanetetracarboxylic acid diimine, N -hydroxyphthalic acid imine, N-hydroxytetrabromophthalimide, N-hydroxytetrachlorophthalimide, N-hydroxychlorophosphonium imine, N-hydroxy humic醯 醯 imine, N-hydroxytrimellitic acid quinone imine, N, N'-dihydroxy benzalkonium diimide, N, N'-dihydroxynaphthalene tetracarboxylic acid diimine, α, --diethoxycarbonyl-N-hydroxysuccinic acid quinone imine, N-hydroxy-α,β-bis(propoxy oxy) succinic acid succinimide, N-hydroxy-α,β-bis(pentanyl) Oxy) succinic acid succinimide, N-hydroxy-α, β-bis(lauryl methoxy) succinic acid succinimide, α,β-bis(benzyl methoxy)-N-hydroxysuccinic acid yttrium Amine, N-hydroxyl 4-methoxycarbonylphthalimide, 4-ethoxycarbonyl-N-hydroxyphthalimide, N-hydroxy-4-pentyloxycarbonylphthalimide 4-dodecyloxy-N-hydroxycarbonylphthalimide, N-hydroxy-4-phenoxycarbonylphthalimide, N-hydroxy-4,5-bis(methoxy Carbonyl) phthalimide, 4,5-bis (ethoxycarbonyl) -N-hydroxyphthalic acid imine, N-hydroxy-4,5-bis(pentyloxycarbonyl)phthalimide, 4,5-bis(dodecyloxycarbonyl)- X in the formula (1) such as N-hydroxyphthalic imine, N-hydroxy-4,5-bis(phenoxycarbonyl)phthalimide, etc. is -OR group and R is hydrogen a compound of an atom; a compound corresponding to these compounds wherein R is an indenyl group such as an ethyl fluorenyl group, a propyl fluorenyl group or a benzhydryl group; N-methoxymethyloxyphthalimide, N-(2) X in the formula (1) such as -methoxyethoxymethyloxy) phthalimide, N-tetrahydropiperanyloxyphthalimide, etc. is -OR group and R a compound which forms a group of an acetal or a hemiacetal with a hydroxyl group; N-methylsulfonyloxyphthalimide, N-(p-toluenesulfonyloxy) phthalimide, etc. X in the formula (1) is a -OR group and R is a sulfonyl compound; in the formula (1) of a sulfate, a nitrate, a phosphate or a borate of N-hydroxyphthalimide X is a compound of the -OR group and R is a group obtained by removing an OH group from a mineral acid.

Among the preferred quinone imine compounds, representative examples of the compound having a cyclic quinone imine skeleton having 6 members include N-hydroxypentadienimide, N-hydroxy-α, α-dimethyl group. Pentamethylene imine, N-hydroxy-β, β-dimethylpentadienimide, N-hydroxy-1,8-decahydronaphthalene dicarboxylate, N,N'-dihydroxy-1 , 8; 4,5-decahydronaphthalene tetracarboxylic acid diimine, N-hydroxy-1,8-naphthalenedicarboxylic acid quinone imine (N-hydroxynaphthoquinone imine), N, N'- a compound of the formula (1) wherein divalent imine-1,8;4,5-naphthalenetetracarboxylic acid diimenimine is an -OR group and R is a hydrogen atom; R corresponding to these compounds is an ethyl group a compound of a mercapto group such as a propyl fluorenyl group or a benzhydryl group; N-methoxymethyloxy-1,8-naphthalene dicarboxylic acid quinone imine, N,N'-bis(methoxymethyl oxygen) X in the formula (1) such as -1,8; 4,5-naphthalenetetracarboxylic acid diimine or the like is -OR And R is a compound which can form a acetal or hemiacetal group with a hydroxyl group; N-methylsulfonyloxy-1,8-naphthalene dicarboxylate imine, N,N'-bis(methylsulfonate) a compound of the formula (1) wherein X is -OR group and R is a sulfonyl group; N-hydroxy-1,8-naphthalene Formula (1) of a sulfonium dicarboxylate or a sulfate, nitrate, phosphate or borate ester of N,N'-dihydroxy-1,8;4,5-naphthalenetetracarboxylic acid diimine The compound in which X is an -OR group and R is a group in which an OH group is removed from a mineral acid is used.

In the above quinone imine compound, a compound in which X is a -OR group and R is a hydrogen atom (N-hydroxy quinone imine compound) can be reacted by a conventional hydrazine imidization reaction, for example, by reacting an acid anhydride with a hydroxylamine, and an acid anhydride. The open-loop and closed-loop of the base are produced by a method of ruthenium imidization. Further, in the above quinone imine compound, a compound in which X is a -OR group and R is a protecting group of a hydroxyl group can be used by a compound (N-hydroxyquinone imine compound) corresponding to R as a hydrogen atom, and a conventional protecting group can be used. The reaction was introduced and introduced into a desired protective group to produce. For example, N-acetoxyphthalimide can be produced by reacting N-hydroxyphthalimin with acetic anhydride or by reacting a hydrazine halide in the presence of a base.

A particularly preferred quinone imine compound having a cyclic quinone imine skeleton comprises an N-hydroxy quinone imine compound derived from an aliphatic polycarboxylic anhydride or an aromatic polycarboxylic anhydride (for example, N-hydroxysuccinimide (SP value) :33.5[(MPa) ^1/2 ]), N-hydroxyphthalimide (SP value: 33.4 [(MPa) ^1/2 ]), N, N'-dihydroxy pyromellitic acid diterpenoid Imine, N-hydroxypentadienimide, N-hydroxy-1,8-naphthalene dicarboxylate imine, N,N'-dihydroxy-1,8; 4,5-naphthalenetetracarboxylic acid diterpene An imine or the like) and a compound obtained by introducing a protective group to a hydroxyl group of the N-hydroxyquinone imine compound.

The quinone imine compound having a cyclic quinone imine skeleton may be used alone or in combination of two or more. The quinone imine compound can be produced in the reaction system, and in the present invention, for example, the trade name "N-hydroxyphthalimide" (manufactured by Wako Pure Chemical Industries, Ltd.), trade name " A commercially available product such as N-hydroxysuccinic acid ylide (manufactured by Wako Pure Chemical Industries, Ltd.).

Further, the quinone imine compound having a cyclic quinone imine skeleton can also be used in the form of a carrier (for example, a porous carrier such as activated carbon, zeolite, ceria, cerium oxide-alumina, or bentonite).

The amount of the quinone imine compound having a cyclic quinone imine skeleton is, for example, about 0.0000001 to 1 mol, preferably 0.00001 to 0.5 mol, and particularly preferably 0.0001 to the hydrocarbon 1 mol as the reaction substrate. 0.4 mole, the best is 0.05~0.4 m. By using the quinone imine compound having a cyclic quinone imine skeleton in the above range, the oxidation reaction can be promoted at an excellent reaction rate.

The quinone imine compound having a cyclic quinone imine skeleton can be supplied to the reaction system in the form of a solution dissolved in a solvent. Further, as the solvent, for example, those described in the above-mentioned "hydrocarbon" item which is inert to the oxidation reaction can be used.

[oxidation reaction]

In the present invention, the reaction temperature in the oxidation reaction can be appropriately selected depending on the kind of the hydrocarbon as the reaction substrate, the type of the target product, and the like, and is, for example, about room temperature to about 200 ° C, preferably 50 to 150 ° C, particularly preferably 60~130 °C. The reaction can be carried out under normal pressure or under pressure, and reacted under pressure. In the case, it is usually about 0.1 to 10 MPa (preferably 0.15 to 8 MPa, particularly preferably 0.5 to 8 MPa). In the present invention, since oxygen as an oxidizing agent is used together with ozone, the oxidation reaction can be smoothly carried out under normal pressure (0.1 MPa).

In the present invention, the flow rate (ml/min) of the gas supplied from the gas introduction flow path 4 to the gas-liquid mixing unit 5 and the flow rate of the liquid supplied from the liquid introduction flow path 15 to the gas-liquid mixing unit 5 (ml/min) The ratio of the gas-liquid mixture is such that the reaction can be efficiently carried out, and the former is usually the gas flow rate / the latter (liquid flow rate) = 2/8 to 8/2, preferably The former/the latter = 3/7~7/3, and the better is the former/the latter = 4/6~6/4.

The linear velocity (LV) of the gas-liquid mixture in the flow reactor is, for example, 50 to 10,000 cm/min, preferably 100 to 5,000 cm/min, and preferably 100 to 1000 cm/min, based on the reaction efficiency and thermal efficiency. minute.

Further, the linear velocity (LV) (cm/min) of the above gas-liquid mixture was determined by the following formula.

LV=(Q1+Q2)/S

Q1: Supply amount of gas (flow rate of gas flowing through the gas introduction flow path 4) (cubic centimeters per minute)

Q2: the supply amount of the liquid (the flow rate of the liquid flowing through the liquid introduction flow path 15) (cubic centimeters per minute)

S: cross-sectional area of the flow reactor (square centimeters)

The above S system is obtained by the following formula.

S=(D/2) ² ×π

D: inner diameter of the flow reactor (cm)

The reaction mixture discharged from the flow reactor 7 is separated into a gas and a liquid at the gas-liquid separator 9 as described above. The separated liquid system is recovered by the liquid recovery flow path 16. Further, when the unidirectional conversion rate is low, at least a portion of the liquid can be recycled to the reaction system. The reaction liquid may be recovered from the liquid recovery flow path 16 after the operation of recycling the liquid separated by the gas-liquid separator 9 to the reaction system for a predetermined period of time; or, in a continuous manner: one side of the liquid recovery flow path 16 A part of the liquid separated by the gas-liquid separator 9 (recovered on one side) is continuously or intermittently taken, and the remaining liquid is recycled to the reaction system.

The recovered liquid can be obtained by a separation means such as filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, or the like, or a combination of these.

[Examples]

Hereinafter, the present invention will be more specifically described based on the examples, but the present invention is not limited by the examples.

Example 1

The gas introduction line (line A), the reaction liquid introduction line (reaction liquid circulation line; line B), the SUS316 tube (line C; inner diameter 1 mm, full length 3 meters) as a flow reactor, gas liquid via Teflon The mixer (inner diameter 1 mm) is connected. Further, one end of the line B not connected to the gas-liquid mixer and one end of the line C not connected to the mixer were connected to a 100-ml receiver (manufactured by SUS316), and assembled into an oxidation reaction reactor.

Next, 15 g of tetradecane was fed into the receiver, and stirred at room temperature, and 2 m of the line C was immersed in an oil bath and heated to 90 °C. Thereafter, air containing ozone was supplied from the line A to the mixer at a flow rate of 6 ml/min, while the reaction liquid (tetradecane and its oxide) was supplied from the line B to the mixer at a flow rate of 3 ml/min. This produces a gas-liquid mixed flow inside the line C while circulating the reaction liquid. Further, the reaction liquid (tetradecane and its oxide) is circulated from the receiver through the line B, the mixer, and the line C at the receiver.

Fig. 2 is a schematic flow chart showing the reactor for the oxidation reaction in the present embodiment. 21 is a gas introduction line (line A), 22 is a reaction liquid introduction line (line B), and is connected to a gas-liquid mixer of 24. Thereafter, a gas-liquid mixed flow was generated by a gas-liquid mixer, and tetradecane (and its oxide) was oxidized in a flow reactor (line C) of 23, and the reaction liquid was supplied to a receiver of 25.

After the lapse of 8 hours, the pump was stopped, and the liquid composition inside the receiver was analyzed by a gas chromatograph (column: 007-FFAP). As a result, the formation of tetradecanol and tetradecanone was confirmed. Further, the conversion ratio (matrix conversion ratio) of tetradecane was determined from the area ratio of tetradecane to the product. The results are summarized in Table 1.

Examples 2 and 3

The same operation as in Example 1 was carried out except that the reaction temperature was changed to 105 ° C, and the conversion of tetradecane was determined (Example 2). Further, the same operation as in Example 1 was carried out except that the reaction temperature was changed to 115 ° C, and the conversion of tetradecane was determined (Example 3). The results are summarized in Table 1.

Comparative example 1

The same operation as in Example 1 was carried out except that the reaction tube was replaced with a Teflon tube instead of the SUS316 tube, and as a result, no conversion of tetradecane was observed. The results are summarized in Table 1.

Example 4~10

The same operation as in Example 1 was carried out except that the tetradecane was changed to the hydrocarbons shown in Table 1, and the conversion ratio of each was determined (Examples 4 to 10). The results are summarized in Table 1.

[Industrial availability]

Since the reactor for the oxidation reaction of the present invention has the above-described configuration, the hydrocarbon can be effectively oxidized, and the cost of the catalyst can be reduced, and the flow reactor due to the oxidation reaction is less deteriorated, so that the production can be high. The corresponding oxide is obtained sexually.

1‧‧‧hydrocarbon supply flow path

2‧‧‧Oxygen introduction flow path

3‧‧‧Ozone generator

4‧‧‧ gas introduction flow path

5‧‧‧ gas-liquid mixing section (gas-liquid mixer)

6‧‧‧ gas-liquid mixture flow path

7‧‧‧Flow reactor

8‧‧‧Reaction mixture flow path

9‧‧‧ gas-liquid separator

10‧‧‧Liquid circulation flow path

11‧‧‧ gas circulation flow path

12‧‧‧Ozone Decomposer

13‧‧‧Exhaust line

14‧‧‧Imineimide compound introduction flow path

15‧‧‧Liquid introduction flow path

16‧‧‧Liquid recovery flow path

Claims (7)

A reactor for an oxidation reaction, which is a reactor for an oxidation reaction comprising: a liquid introduction flow path for introducing a liquid containing a hydrocarbon as a reaction substrate; and a gas introduction flow path for introducing a gas containing oxygen and ozone; a gas-liquid mixing unit that mixes the liquid introduced from the liquid introduction channel with the gas introduced from the gas introduction channel; and a flow reactor characterized in that the inner wall of the flow reactor is made of iron. A flow reactor, or a flow reactor filled with iron-containing powder inside. A reactor for an oxidation reaction according to claim 1, wherein a gas-liquid separator is provided on a downstream side of the flow reactor. The reactor for an oxidation reaction according to claim 2, further comprising a circulation flow path for recycling at least a part of the liquid separated by the gas-liquid separator to the gas-liquid mixing portion or an upstream portion thereof. The reactor for an oxidation reaction according to claim 2 or 3, further comprising a circulation flow path for recycling at least a part of the gas separated by the gas-liquid separator to the gas-liquid mixing portion or an upstream portion thereof. The reactor for an oxidation reaction according to any one of claims 1 to 4, wherein a ruthenium compound introduction channel for introducing a quinone imine compound having a cyclic quinone imine skeleton is provided on the upstream side of the flow reactor. The reactor for an oxidation reaction according to claim 5, wherein the quinone imine compound having a cyclic quinone imine skeleton is a quinone imine compound represented by the following formula (I). [wherein, n represents 0 or 1; X represents an oxygen atom or a -OR group (R represents a hydrogen atom or a protecting group of a hydroxyl group)]. A method for producing an oxide characterized by using a reactor for an oxidation reaction according to any one of claims 1 to 6, wherein a hydrocarbon is oxidized in the presence of oxygen and ozone to obtain a corresponding oxide.